High-level coupled-cluster energetics by merging moment expansions with selected configuration interaction
Abstract
Inspired by our earlier semi-stochastic work aimed at converging high-level coupled-cluster (CC) energetics [J. E. Deustua, J. Shen, and P. Piecuch, Phys. Rev. Lett. 119, 223003 (2017) and J. E. Deustua, J. Shen, and P. Piecuch, J. Chem. Phys. 154, 124103 (2021)], we propose a novel form of the CC(P; Q) theory in which the stochastic Quantum Monte Carlo propagations, used to identify dominant higher-than-doubly excited determinants, are replaced by the selected configuration interaction (CI) approach using the perturbative selection made iteratively (CIPSI) algorithm. The advantages of the resulting CIPSI-driven CC(P; Q) methodology are illustrated by a few molecular examples, including the dissociation of F₂ and the automerization of cyclobutadiene, where we recover the electronic energies corresponding to the CC calculations with a full treatment of singles, doubles, and triples based on the information extracted from compact CI wave functions originating from relatively inexpensive Hamiltonian diagonalizations.
Additional Information
© 2021 Published under an exclusive license by AIP Publishing. Submitted: 22 July 2021; Accepted: 11 October 2021; Published Online: 3 November 2021. This work was supported by the Chemical Sciences, Geosciences and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy (Grant No. DE-FG02-01ER15228 to P.P.), and Phase I and II Software Fellowships awarded to J.E.D. by the Molecular Sciences Software Institute funded by the National Science Foundation (Grant No. ACI-1547580). We thank Dr. Pierre-François Loos and Dr. Anthony Scemama for useful discussions about Quantum Package 2.0 employed in our CIPSI computations. The authors have no conflicts to disclose. Data Availability: The data that support the findings of this study are available within the article.Attached Files
Published - 174114_1_online.pdf
Accepted Version - 5_0064400-acc.pdf
Submitted - 2107-10994.pdf
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Additional details
- Eprint ID
- 111711
- Resolver ID
- CaltechAUTHORS:20211102-194502739
- DE-FG02-01ER15228
- Department of Energy (DOE)
- ACI-1547580
- NSF
- Created
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2021-11-02Created from EPrint's datestamp field
- Updated
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2023-10-05Created from EPrint's last_modified field